WO2007010517A1 - Polymères nanocomposites - Google Patents

Polymères nanocomposites Download PDF

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Publication number
WO2007010517A1
WO2007010517A1 PCT/IE2006/000079 IE2006000079W WO2007010517A1 WO 2007010517 A1 WO2007010517 A1 WO 2007010517A1 IE 2006000079 W IE2006000079 W IE 2006000079W WO 2007010517 A1 WO2007010517 A1 WO 2007010517A1
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Prior art keywords
polymer
nanotubes
kevlar
nanoparticles
fibres
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PCT/IE2006/000079
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English (en)
Inventor
Iouri Kuzmich Gounko
Hugh Hayden
Jonathan Nesbit Coleman
Ian Edward O'connor
Werner Josef Blau
Rowan Blake
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The Provost, Fellows And Scholars Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth, Near Dublin
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Application filed by The Provost, Fellows And Scholars Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth, Near Dublin filed Critical The Provost, Fellows And Scholars Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth, Near Dublin
Priority to EP06766086A priority Critical patent/EP1910220A1/fr
Priority to US11/988,923 priority patent/US20090039308A1/en
Publication of WO2007010517A1 publication Critical patent/WO2007010517A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/08—Processes in which the treating agent is applied in powder or granular form

Definitions

  • the present invention relates to a method for producing modified polymer fibres.
  • US 6,599,631 (WO02058928) describes inorganic particle/polymer composites that involve chemical bonding between the elements of the composite. These compositions include a polymer having side groups chemically bonded to inorganic particles. The composite composition can also include chemically bonded inorganic particles and ordered copolymers. Various electrical, optical and electro-optical devices can be formed from the composites.
  • carbon nanotubules (often termed carbon nanotubes because of their diminutive dimensions) have the potential to be used in similar ways to carbon fibres.
  • the structure of carbon nanotubes makes their aspect ratio (length/diameter, (LIO)) comparable to that of long fibres.
  • LIO length/diameter
  • the aspect ratio of carbon nanotubes is > 10000.
  • the aspect ratio of carbon nanotubes is generally much greater than that of conventional short fibres, such as short glass fibres and short carbon fibres.
  • the tubes can potentially be lighter than conventional carbon fibres, whilst being stronger and stiffer than the best conventional carbon fibres.
  • carbon nanotubes have great mechanical stiffness, being cited as having tensile modulus in the range of 1000 GPa. Moreover they have been mentioned in connection with new, highly efficient, fracture micro- mechanisms which would prevent pure brittle failure with a concomitant low strain. Thus, carbon nanotubes have been envisaged for use in many applications in recent years (4, 5, 6, 7).
  • a recently reported method for processing carbon nanotubes provides nanotube fibers whose mechanical properties significantly surpass those of ordinary bucky paper (8, 9).
  • the carbon nanotubes are first dispersed in an aqueous or non-aqueous solvent with the aid of a surfactant.
  • a narrow jet of this nanotube dispersion is then injected into a rotating bath of a more viscous liquid in such a way that shear forces at the point of injection cause partial aggregation and alignment of the dispersed nanotube bundles.
  • This viscous liquid contains an agent or agents, which act to neutralize the dispersing action of the surfactant.
  • the jet of dispersed nanotubes is rapidly coagulated into a low-density array of entangled nanotubes, thereby gaining a small (but useful) amount of tensile strength.
  • the wet filament is then washed in water, and the washed filament is subsequently withdrawn from the wash bath and dried.
  • capillary forces collapse the loosely tangled array of nanotubes into a compact thin fiber having a density of about 1.5 gm/cc (close to the theoretical density of a compact array of carbon nanotubes). This total process will henceforth be referred to as the coagulation spinning (CS) process.
  • CS coagulation spinning
  • US 6,682,677 teach a method of forming fibers, ribbons and yarns wherein the carbon nanotubes are first dispersed in an aqueous or nonaqueous solvent with the aid of a surfactant in the coagulation spinning process described above.
  • US 6,764,628 also describes fiber spinning of two polymer compositions wherein one of the compositions contains carbon nanotubes and produces structures such as fibers, ribbons, yarns and films of carbon nanotubes. The polymers are removed and stabilization of the carbon nanotube material is achieved by post-spinning processes.
  • the obtained modulus of the fibres made by this process is 15 GPa or less, which is over an order of magnitude lower than that of the constituent individual nanotubes (about 640 GPa).
  • the method is also very expensive and technically demanding and requires quite specific equipment.
  • a new cost effective method to modify properties polymers using nanomaterials would have valuable potential for a broad range of applications.
  • the modified polymer is washed with an appropriate solvent and dried.
  • solvent is taken to mean a normally non-swelling solvent or a non-swelling mixture of solvents for the polymer
  • the solvent may be selected from any one or more of an alcohol such as ethanol, or ether.
  • the nanotube or nanoparticle suspension comprises nanotube or nanoparticles suspended in a solvent.
  • the solvent may be selected from any one or more of r ⁇ -methyl pyrollidone (NMP), dimethylformamide (DMF), organic amides, amines, ethers, esters, aldehydes, ketones, xylenes and other appropriate organic solvents.
  • NMP r ⁇ -methyl pyrollidone
  • DMF dimethylformamide
  • organic amides organic amides
  • amines organic amines
  • ethers organic amides
  • esters aldehydes
  • ketones aldehydes
  • xylenes xylenes
  • Other appropriate organic solvents are taken to mean a swelling solvent or a mixture of swelling solvents for the polymer.
  • the nanoparticles or nanotubes are selected from any one more of metals, non-metals, metal oxides, metal chalcogenides, metal pnictides, and ceramic materials.
  • the nanotubes are carbon nanotubes.
  • the nanotubes may be selected from single-walled, double-walled or multi- walled nanotubes.
  • the nanotubes are in the form of non- continuous nanotubes.
  • the nanotubes are less than 50nm in length, preferably less than 20nm in length.
  • the nanotubes are approximately 10 ⁇ m (micrometers) in length.
  • the nanotubes comprise a length/diameter aspect ratio of greater than 100.
  • the nanotubes comprise a length/diameter aspect ratio of greater than 10 3 , most preferably of greater than 10 4 .
  • the nanotubes or nanoparticles are introduced/intercalated into the polymer on swelling of the polymer in the nanotube suspension.
  • the nanoparticles are introduced into the polymer, preferably less than 30 % by weight of the nanoparticles are introduced into the polymer, most preferably less than 20 % by weight of the nanoparticles are introduced into the polymer.
  • the polymer is a swellable polymer.
  • the polymer may be in the form of polymeric yarns, fibres, fabrics, ribbons or films.
  • the polymer comprises a fibre and/or film- forming polymer.
  • the polymer may be selected from any one or more of a polyolefin, polyester, polyamide or other polymeric materials.
  • the polyolefin comprises a polymer selected from a polyethylene or a polypropylene.
  • the polymer is KevlarTM.
  • the swelling of the polymer is carried out at room temperature or under heating of from 20°C to 200°C.
  • the swelling of the polymer is carried out by heating under reflux.
  • the swelling of the polymer is carried out under ultrasonic treatment.
  • the ultrasonic treatment may be carried out at room temperature or under heating from 20 0 C to 300°C.
  • the invention also provides a modified polymer whenever prepared by a method as hereinbefore described.
  • the polymer may be a reinforced polymer, a conductive polymer composite, a luminescent polymer composite and/or a magnetic polymer composite.
  • the invention further provides a reinforced polymer comprising a Young's modulus of between 2 and 1 OOOGPa, a strength of between 1 and 1 OGPa and a toughness between 33 and 2000 J/g.
  • the invention also provides a reinforced polymer comprising a Young's modulus of between 2 and 500GPa, a strength of between 1 and lOGPa and a toughness between 33 and 2000 J/g.
  • the invention also provides use of a reinforced polymer prepared by a method of the invention or a polymer as hereinbefore described in the manufacture of any one or more of fishing gear, tyres, safety belts, sewing thread, protective clothing, bullet proof vests, durable man-made fibre, automotive and aircraft materials, cement paste, mortar and concrete.
  • the invention also provides use of a reinforced polymer prepared by a method of the invention or a polymer as hereinbefore described in high tenacity polymeric fibres, films, fabrics and filaments as a replacement for conventional reinforcing agents and additives.
  • the invention further provides use of conductive polymer composites produced by a method of the invention in electrical devices such as thermal sensors, low power circuit protectors, over current regulators, flexible conductive electrodes and/or flexible displays.
  • the invention also provides use of fluorescent polymer composites produced by a method of the invention in smart interactive textiles, sensors and/or as components for optical communications.
  • the invention further provides use of magnetic polymer composites produced by a method of the invention in electromagnetic interference (EMI) shielding such as shielding of medical equipment in hospitals and/or consumer electronics.
  • EMI electromagnetic interference
  • the invention further provides semiconducting and conducting polymer composites.
  • the invention also provides magnetic polymer composites.
  • the invention further provides fluorescent polymer composites.
  • Fig. 1 is a graph showing the sedimentation curves for 0.15g/L solution MWNTs solution in NMP;
  • Fig. 2 are SEM images of the cross section for MWNTs - Kevlar composites.
  • the top image is at a magnification of x 8K, the lower image is at a magnification of x 35K;
  • Fig. 3 are SEM images of Kevlar fibres before a) and after b) treatment with nanotube suspension under ultrasound;
  • Fig. 4 are graphs of the percentage increase of fibres against the time of sonication: a) linear fit and b) log scale;
  • Fig. 5 is a bar chart showing the comparison of an increase in Young's modulus for the different nanotube-Kevlar composites
  • Fig. 6 is a graph showing the stress/strain curves for blank Kevlar fibre (bottom curve) and Kevlar fibre in 0.15 g/1 of nanotube suspension (middle curve) and 0.30 g/1 of nanotube suspension in NMP (top curve);
  • Fig. 7 is a graph of the change in tensile strength against nanotube concentration
  • Fig. 8 is a graph of the change in tensile strength against nanotube mass uptake
  • Fig. 9 are graphs of ultimate tensile strength (UTS) and toughness of polypropylene swollen with MWNTs in xylene and toluene under ultrasound;
  • Fig.10 are cross sectional SEM images of polypropylene swollen in toluene with MWNTs;
  • Fig. 1 1 are conductivity graphs a) of a pure polyethylene film and b) of a polyethylene film swollen in toluene with a 4g/L concentration of nanotubes;
  • Fig. 15 are magnetisation curves for Kevlar fibers swollen using a) Fe 3 O 4 nanoparticles and b) cobalt ferrite nanoparticles.
  • the method provides the ability to modify any preformed polymer fibres ribbons or films by a simple and cost effective swelling procedure.
  • the method provides modified polymer fibres ribbons and films with improved properties. This technology have been used to fabricate new superstrong, conductive, magnetic and fluorescent polymer composites with a broad range of potential applications.
  • Carbon nanotubes, magnetic (Fe 3 O 4 ) and fluorescent (CdTe) nanoparticles suspensions have been utilised to demonstrate the fabrication of new polymer composites.
  • the polymer used is not particularly limited as long as the polymer can be produced in the form of yarns, fibres, fabrics, ribbons or films.
  • the polymer is preferably a polyamide, such as a Kevlar, which is not soluble in the most of common solvents, but can be easily swelled in n-methyl pyrollidone (NMP) or dimethylformamide (DMF).
  • NMP n-methyl pyrollidone
  • DMF dimethylformamide
  • Multiwalled carbon nanotubes from Nanocyl can be dispersed in NMP by sonicating them for 30 min or more using an ultrasonic bath proving a good dispersion of nanotubes in the solvent.
  • Suspensions of magnetic (Fe 3 O 4 ) and fluorescent semiconducting (CdTe) nanoparticles can be prepared similarly.
  • Kevlar braided yarn can be placed in the carbon nanotube or nanoparticle suspension in NMP and the mixture can be sonicated for 30 or more minutes. The solution can be then heated under reflux for up to 24 hours. Alternatively, Kevlar fibre may be left to swell in the nanotube suspension in NMP at ambient temperature for up to 24 hours or left in the suspension under ultrasound (ultrasonic bath) for up to 12 hours. The Kevlar yarn can be removed and washed in ethanol several times to remove any residual nanotubes or nanoparticles from the Kevlar surface. The Kevlar can be dried at room temperature or in oven at 100 °C. Incorporation of the nanotubes during the swelling leads to a significant improvement in the mechanical properties of the blends.
  • Kevlar Young's modulus and tensile strength of Kevlar can be increased at least twofold (over 200 %) by a simple swelling the Kevlar fibres in 0.3 g/L suspension of carbon nanotubes in n-methyl pyrollidone (NMP). The high increase may be achieved at the higher concentrations of carbon nanotubes. Incorporation of the nanotubes also increases electrical conductivity of polymer. Incorporation of magnetic nanoparticles results in magnetic composites, while incorporation of fluorescent semiconducting nanoparticles results in new fluorescent polymer composites.
  • the reinforced polymers of the invention are useful in a wide variety of applications involving the reinforcement of polymers, including for example use in fishing gear, tyres, safety belts, sewing thread, protective clothing, durable man-made fibre, and in cement paste, mortar or concrete.
  • the reinforced polymers are particularly useful in high tenacity polymeric fibres and filaments as a replacement for conventional reinforcing agents.
  • the conductive polymer composites are useful in different electrical devices as thermal sensors, low power circuit protectors, over current regulators, flexible conductive electrodes and flexible displays.
  • Carbon nanotubes are used for reinforcement in the invention.
  • carbon nanotubes it is meant carbon tubes having a structure related to the structure of Buckminsterfullerene (C 60 ).
  • the carbon nanotubes used in the present invention need not necessarily have dimensions of the order of nanometers in size. The dimensions of the nanotubes may be much greater than this.
  • the nanotubes are of a diameter from 1 -50 run, more preferably about 20 nm.
  • the nanotubes are 1 ⁇ m or more in length, more preferably about 10 ⁇ m in length.
  • the nanotubes are endowed with a high aspect ratio, having a length/diameter (LfD) of 100 or more, preferably 10 3 or more and most preferably 10 4 or more. Therefore, composites comprising these nanotubes should, when the nanotubes are properly aligned, have mechanical properties which behave similarly to those of composites containing continuous carbon fibres.
  • LfD length/diameter
  • Increasing the aspect ratio of the nanotubes leads to enhanced strength and stiffness in the composite.
  • a long aspect ratio and a greater increase in mechanical properties may be achieved by the functionalisation of the polymeric matrix as well as the nanotubes to give good covalent binding and ensure good interfacial shear strength.
  • the concentration of nanotubes in the composites is strongly dependant on their solubility and an ability to form a stable suspension in a chosen solvent.
  • Use in the present invention of effectively non-continuous nanotubes (short in comparison to regular carbon fibres) rather than continuous fibres, allows access to typical processing techniques. These techniques permit high throughput production and fabrication of high quality, fibre shaped composites.
  • polymer composites comprising nanotubes can provide the best of both worlds, high mechanical strength and ease of processing.
  • the quantity of carbon nanotubes added to a given quantity of polymer is not particularly limited. Typically less than 50% by wt of carbon nanotubes or less is added to the polymer. Preferably 30% by wt or less and more preferably 20% by wt or less of nanotubes is added. It is most preferred that 5% by wt or less of nanotubes is added.
  • a very small quantity of nanotubes is capable of beneficially affecting the properties of a polymer. Very small quantities of nanotubes may be used, depending on the intended use of the polymer. However, for most applications it is preferred that 0.1% wt. of nanotubes or greater is added.
  • the present invention extends to a reinforced polymer obtainable according to the methods of the present invention.
  • the reinforced polymer fibres of the present invention have superior mechanical properties, as has been discussed above. It is preferred that the modulus, the tensile strength and/or the toughness of fibres formed from the present reinforced Kevlar are greater by at least 50%, as compared with the equivalent properties of the same polymer not comprising carbon nanotubes after undergoing the same stretching procedure.
  • any additives typically introduced into polymers may be included in the reinforced polymers of the invention, provided that the additives do not prevent the enhanced mechanical properties of the present polymers being obtained.
  • additives such as pigments, anti-oxidants, UV-protective HALS (Hindered Amine Light Stabilisers), lubricants, anti-acid compounds, peroxides, grafting agents and nucleating agents may be included.
  • the fluorescent nanoparticles can include any H-VI types colloidal nanoparticles.
  • Magnetic nanoparticles can include any metal, alloy or metal oxide based magnetic nanoparticles.
  • the fluorescent polymer composites are useful in smart interactive textiles, sensors and as components for optical communications.
  • the magnetic polymer composites are useful in electromagnetic interference (EMI) shielding of medical equipment in hospitals, computers and consumer electronics.
  • EMI electromagnetic interference
  • Curly multiwalled carbon nanotubes were obtained from Nanocyl company. Yellow Kevlar 129 was supplied as a branded Yarn by Du Pont.
  • Amino functionalised carbon nanotubes were prepared via a Diels-Aler reaction using 1,4-diamino tetrazine (datz).
  • the MWNTs (1.0xl0 "2 g) were sonicated in ethanol (20 ml) for 15 minutes, to ensure a good dispersion.
  • Datz (0.01 g) was added to the mixture and it was heated under reflux for up to 48 hrs. Each time the samples were washed twice with THF (10 ml) three times with ethanol (10ml) and dried in vacuum.
  • Kevlar protected acid purified (KPAF) nanotubes The non-pure arc discharge nanotube material (0.2g) was placed into a round bottom flask containing nitric (70 ml) and sulphuric (20 ml) acid. The Kevlar (0.6g) was added and the mixture was sonicated for 30 minutes. Then it was heated under reflux for 12 hours. After that the mixture was allowed to cool to room temperature and the solution was transferred to a narrow sample holder. The nanotubes were allowed to settle for three hours before the excess acid was decanted. The remaining solution was then slowly neutralised by the addition of NaHCO 3 in water. After the neutralisation process, the solution was allowed to settle overnight before the water was decanted off. The product was washed several times with water and dried in vacuum to give 0.5g of KPAP nanotubes.
  • Kevlar has a very low solubility in all common solvents. It is extremely difficult to process and study this material and the nanocomposite materials by the usual methods.
  • Kevlar is not soluble in NMP without CaCl 2 additives, while nanotubes have a very good solubility in NMP.
  • Sedimentation studies of 0.15g/L solution MWNTs solution in NMP were carried out. The experiment was performed by monitoring the absorbance of the solution over time using 4 lasers.
  • Nanotubes stay in solution without any visible precipitation for at least 2 hours (Fig. 1). Then only a very small (-6.7%) amount of nanotubes precipitated during 3 days. This allowed us to prepare a stable colloidal solution of carbon nanotubes, which then served as a medium to swell the Kevlar fibres using ultrasound and heating. Nanotubes form a stable colloidal suspension in NMP.
  • Kevlar-nanotube composite The process of the preparation of Kevlar-nanotube composite was carried out in three stages. First Kevlar fibres were cut into strips about 30 cm long and washed in acetone to remove any industrial grease/residue, the sample was then dried, and weighed. The second step was to mix the Kevlar and the nanotubes in NMP, by sonicating them for 30 minutes in the sonic bath. This was done to disperse the nanotubes and to open up the Kevlar fibre, from being tightly wound to loose fibres. The final step, the heating of the mixture under reflux for several hours, before the fibres are removed and washed by sonicating in ethanol for 1-2 minutes. The presence of nanotubes inside in Kevlar fibres have been confirmed by SEM images (Fig. 2). The five types of nanotubes used for the preparation the nanotube-Kevlar composites are shown in Table 1 below. Table 1
  • Kevlar-nanotube composites a study was carried out to see how many nanotubes became adhered to the Kevlar matrix.
  • a series of reaction conditions using the different nanotubes were made up in 20ml of NMP.
  • a pre-weighed Kevlar sample was added to each NT solutions and sonicated for 30 minutes, before being heated under reflux for up to 24 hours. The samples were then washed, dried and weighed. The concentration of nanotubes in each Kevlar sample was calculated. The highest intake of nanotubes was found to take place during the first hour of heating. Longer heating does not increase the nanotube content too much.
  • Kevlar-nanotube composite using ultrasound was carried out similarly above in three stages.
  • First Kevlar fibres were cut into Im long strips and weighed.
  • the second step was to mix the Kevlar and the nanotubes in NMP, by sonicating them for a certain period of time in the sonic bath.
  • Many different techniques were tried to get the optimum results including different sonication times from 5 minutes up to 4 hours. Also it was tried using varying concentrations, 0.15g/l up to 1.5 g/1.
  • concentrations 0.15g/l up to 1.5 g/1.
  • Diffusion can, in general, be characterized by an average displacement from the starting point, x, that varies in time, /, as x is proportional to (Dt) 112 , where D is the diffusion coefficient.
  • D is the diffusion coefficient.
  • Tensile modulus and tensile strength of Kevlar-nanotube composites have been measured using Zwick 100 tensile tester or using DMTA machine. Each fibre 0 was placed in the Zwick holder, and each end was tied. The fibre was then pulled using a 10OkN pulling detector. A measurement of the fibres strength, was plotted against force applied, and from this the tensile modulus was calculated. Each measurement was repeated 3 times and an average Young's modulus was taken. 5
  • Kevlar samples modified with Nanocyl MWNTs showed an increase in the Young's modulus by to a factor of 2.3.
  • the NH 2 -MWNT- Kevlar composites were found to give an increase in Young's 0 modulus up to 2.7 times, when compared to the original Kevlar sample. These results are comparable to the Nanocyl MWNTs-Kevlar composites, but there is higher intake percentage of nanotubes for datz-MWNT-Kevlar composites.
  • Kevlar composites comprising Kevlar coated 5 arc-discharge nanotubes. These composites demonstrated an increase in Young's modulus up to 2.8 times. It appears that the Kevlar coated arc discharge nanotubes have a stronger interaction with the Kevlar matrix providing an efficient stress transfer between Kevlar fibres and nanotubes.
  • the results on the mechanical testing for different Kevlar-nanotube composites are shown in Fig. 5 and in Table 3 below.
  • Kevlar-nanotube composite 10 is 10 microns thick.
  • the Kevlar-nanotube composites were tested using DMTA machine.
  • the comparative stress/strain curves for blank Kevlar fibre and Kevlar fibre in 0.15 and 0.30 grams of Nanocyl nanotubes per litre of NMP are shown Fig. 6.
  • Kevlar fibre 15 Kevlar fibre. Calculated toughness for the Kevlar-nanotube composites was more than 3 times higher than one for the original Kevlar fibre.
  • the graph in Fig. 7 shows how the tensile strength varies with changing concentration for the single fibres. Each sample was sonicated for 30 minutes. The value at 0 g/1 corresponds to the untreated Kevlar (blank). The literature value of blank Kevlar has already been shown to be 3.3 to 3.5 Gpa and this experiment agrees with this value. We can see an increase from this value to a maximum mean value of 5.1 Gpa. This shows approximately a 45% increase in the tensile strength of the single fibres.
  • Fig. 8 Dependence of tensile strength of Kevlar-nanotube composites from carbon nanotube mass % uptake is shown in Fig. 8. As we can see the highest increase in strength (-5.1 GPa) is achieved at 1 mass % of carbon nanotube uptake.
  • Kevlar fibre 1 meter was added to a solution of CdSe nano-particles in 20 ml of NMP. The mixture was then sonicated using the sonic tip for 30 mins at 20% tip power. The solution was then removed from the sonic tip and placed in the sonic bath where it was sonicated for another 1 hr. The Kevlar was then removed and washed in ethanol.
  • Fig. 12 Confocal microscopy images of the luminescent Kevlar- nanoparticles composites are shown in Fig. 12.
  • the image on the left shows a single snap shot of the quantum dots luminescing in Kevlar.
  • the image on the right is an average of images taken at different focal points through the fibre. This image shows that the dots are luminescing through the entire Kevlar fibre.
  • the modified fibres were then cut using a blade and the cross-section images of the samples were taken using fluorescent confocal microscope (Fig. 13). As it can be seen in the two images, a single Kevlar fibre which is cut at the end contains luminescent nanoparticles in the centre.
  • the polymer composites of the invention provide a number of advantages as follows:-
  • the method of the invention is a very cost effective technique for providing modified polymers.
  • the method is based on a simple polymer swelling in nanotubes or nanoparticles suspension. It does not require any initial chemical modification or pre-treatment of nanoparticles or nanotubes and polymer and their purification.
  • a standard commercially available polymer in the form of yarns, fibres, fabrics, ribbons or films may be used with an appropriate organic solvent or a mixture of solvents, which are swelling solvents for the polymer. This provides a suspension for nanoparticles or nanotubes which is suitable for the swelling of the selected polymer material. Common solvents for polymer swelling are used.
  • the method allows for all the processes to be carried out at room temperature if necessary and the method does not require the use of any expensive and sophisticated equipment.
  • the method is very universal. It may be developed for any polymeric material, which is able to swell. It may be used for different types of nanoparticles and nanotubes and can result in a very broad range of materials with a number of different potential applications.
  • the method may be easily developed for use in industry.
  • the technique may be easily integrated into modern technologies for polymer fibre or textile modification for example it can be easily implemented using existing fibre or textile colouring techniques and equipment. Therefore the method should reach manufacturing qualification and acceptance more quickly than other alternative approaches.

Abstract

La présente invention concerne des polymères modifiés préparés par l’emploi d’un nanotube ou d’une suspension de nanoparticules, l’adjonction d’un polymère préformé, le gonflement du polymère préformé dans la suspension et l’isolement du polymère modifié de la suspension. Le polymère peut être un polymère dilatable ayant la forme de fils, fibres, toiles, rubans ou films polymériques. Le gonflement peut être réalisé à l’aide d’un traitement par ultrasons.
PCT/IE2006/000079 2005-07-22 2006-07-24 Polymères nanocomposites WO2007010517A1 (fr)

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EP06766086A EP1910220A1 (fr) 2005-07-22 2006-07-24 Polymères nanocomposites
US11/988,923 US20090039308A1 (en) 2005-07-22 2006-07-24 Nanocomposite polymers

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EP1978152A1 (fr) * 2007-04-03 2008-10-08 Commissariat A L'energie Atomique Procede de modification de fibres d'aramide et procede de teinture de ces fibres
US7666327B1 (en) * 2007-05-22 2010-02-23 Oceanit Laboratories, Inc. Multifunctional cementitious nanocomposite material and methods of making the same
US7713448B1 (en) * 2007-08-21 2010-05-11 Oceanit Laboratories, Inc. Carbon nanomaterial dispersion and stabilization
EP2213699A1 (fr) * 2009-01-30 2010-08-04 Bayer MaterialScience AG Procédé d'introduction de particules de carbone dans une couche de surface en polyuréthane
EP2228402A1 (fr) * 2009-03-11 2010-09-15 The Provost, Fellows and Scholars of the College of the Holy and Undivided Trinity of Queen Elizabeth near Dublin Composites de carbone-carbone
EP2315661A1 (fr) * 2008-07-25 2011-05-04 Applied Nanotech Holdings, Inc. Nanocomposites renforcés de nanotubes de carbone
CN102660097A (zh) * 2012-04-11 2012-09-12 上海交通大学 一种增强聚乙烯醇复合物的制备方法
EP2553007A1 (fr) * 2010-03-26 2013-02-06 University Of Hawaii Résines renforcées par des nanomatériaux et matériaux apparentés
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WO2015049067A3 (fr) * 2013-10-02 2015-07-16 The Provost, Fellows, Foundation Scholars, And The Other Members Of Board, Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth, Near Dublin Capteurs de mouvement corporel sensibles, à haute sollicitation, haut rendement, faits de composites conducteurs à base de nanomatériau/caoutchouc
EP2511322B1 (fr) 2009-12-12 2017-03-29 Taiyo Nippon Sanso Corporation Particules résineuses composites et procédé pour produire celles-ci
US10435519B2 (en) 2009-01-20 2019-10-08 Taiyo Nippon Sanso Corporation Composite resinous material particles and process for producing same

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EP2315661A1 (fr) * 2008-07-25 2011-05-04 Applied Nanotech Holdings, Inc. Nanocomposites renforcés de nanotubes de carbone
EP2315661A4 (fr) * 2008-07-25 2013-01-09 Applied Nanotech Holdings Inc Nanocomposites renforcés de nanotubes de carbone
US10435519B2 (en) 2009-01-20 2019-10-08 Taiyo Nippon Sanso Corporation Composite resinous material particles and process for producing same
WO2010086094A1 (fr) * 2009-01-30 2010-08-05 Bayer Materialscience Ag Procédé d'incorporation de particules de carbone dans une couche de surface en polyuréthane
EP2213699A1 (fr) * 2009-01-30 2010-08-04 Bayer MaterialScience AG Procédé d'introduction de particules de carbone dans une couche de surface en polyuréthane
WO2010102819A1 (fr) * 2009-03-11 2010-09-16 The Provost, Fellows And Scholars Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth Composites carbone-carbone
EP2228402A1 (fr) * 2009-03-11 2010-09-15 The Provost, Fellows and Scholars of the College of the Holy and Undivided Trinity of Queen Elizabeth near Dublin Composites de carbone-carbone
EP2511322B1 (fr) 2009-12-12 2017-03-29 Taiyo Nippon Sanso Corporation Particules résineuses composites et procédé pour produire celles-ci
EP2553007A1 (fr) * 2010-03-26 2013-02-06 University Of Hawaii Résines renforcées par des nanomatériaux et matériaux apparentés
EP2553007A4 (fr) * 2010-03-26 2014-11-19 Univ Hawaii Résines renforcées par des nanomatériaux et matériaux apparentés
US9120908B2 (en) 2010-03-26 2015-09-01 University Of Hawaii Nanomaterial-reinforced resins and related materials
US9051216B1 (en) 2010-04-20 2015-06-09 Oceanit Laboratories, Inc. Highly durable composite and manufacturing thereof
CN102660097A (zh) * 2012-04-11 2012-09-12 上海交通大学 一种增强聚乙烯醇复合物的制备方法
CN102660097B (zh) * 2012-04-11 2013-07-10 上海交通大学 一种增强聚乙烯醇复合物的制备方法
WO2015049067A3 (fr) * 2013-10-02 2015-07-16 The Provost, Fellows, Foundation Scholars, And The Other Members Of Board, Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth, Near Dublin Capteurs de mouvement corporel sensibles, à haute sollicitation, haut rendement, faits de composites conducteurs à base de nanomatériau/caoutchouc
US10251604B2 (en) 2013-10-02 2019-04-09 The Provost, Fellows, Foundation Scholars, And The Other Members Of Board, Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth, Near Dublin Sensitive, high-strain, high-rate, bodily motion sensors based on conductive nano-material-rubber composites

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